Anthraquinone derivative.



.new anthracene derivatives.

UNITED STATES PATENT OFFICE.

PAUL THOMASOHEWSKI, OF ELBERFELD, GERMANY, ASSIGNOR TO FARBENFAB-RIKEN VORM. FRIEDR. BAYER & 00., OF ELBERFELD, GERMANY, A CORPORATION OF GERMANY.

ANTHRAQUINONE DERIVATIVE.

Specification of Letters Patent.

T all whom it may concern:

Be it known that 1, PAUL THOMASOHEW- sKI, doctor of philosophy, chemist, citizen of the German Empire, residing at Elberfeld, Germany, Kingdom of Prussia, have invented new and useful Improvements in Anthraquinone Derivatives, of which the following is a specification.

My invention relates to the production of They can be obtained by condensing aminoanthrapyridons with halogen substituted anthrapyridons or with halogen substituted anthraquinones or by condensing halogen substituted anthrapyridons with aminoanthraquinones and they yield with the exception of the condensation product from 4-amino-1-anthrapyridon and 4-bromo-1-anthrapyridon on treatment with alkaline reducing agents vats suitable for dyeing and printing vegetable fibers. They can also be converted into sulfonic acids and are then all suitable for dyeing wool from an acid bath. The sulfonic acids with the exception of the, one obtained from the condensation product of 4-amino-1-anthrapyridon with 4-bromo-1- vanthrapyridon are also capable of forming vats suitable for dyeing and printing but the shades obtained from them are bluer in tint.

The new condensation products are dark powders soluble in hot quinolin and in concentrated sulfuric acid; dyeing in the shape of their suli'onio acids wool from acid baths from orange to red and blue shades.

The invention is illustrated by the following exam les, the parts being by weight:

Exarnp e I.A mixture of 150 parts of 4 brorno 1 anthrapyridon (obtainable by treating 1 acetylmethylamino 4 bromoanthraquinone with alkali according to the process described in United States Patent 853041), 100 parts of Q-aminoanthraquinone, 100 parts of calcium hydroxid, 5 parts of chlorid of copper and 2000 parts of naphthalene is boiled for three hours. The roduct separated in the melt is filtered ofi wlth suction on a hot filter, washed successively with alcohol, dilute hydrochloric acid and water. The product is then further purified by crystallization from anilin. It has the formula:

It is after being dried and pulverized a brown powder soluble in hot quinolin with a crimson red color and in concentrated sulfuric acid with a violet color. It forms an orange vat with alkaline hydrosulfite which vat dyes cotton fast red shades. Its sulfonic acid dyes wool from acid baths red shades.

Example II.A mixture of 100 parts of 4- amino-l-anthrapyridon (obtainable by treating 1 acetylmethylamino 4 aminoanthraquinone with alkali), 100 parts of 4-bromol-anthrapyridon (obtainable by treating 1- acetylmethylamino 4 bromoanthraquinone with an alkali according to the process described in United States Patent 853041), 100 parts of anhydrous sodiuni acetate, 5 parts of chlorid of copper and 2000 parts of naphthalene is boiled for two hours. The new product separates in dark violet needles. It is filtered off with suction on a hot filter and washed with alcohol and water. tion which occurs is probably explained by the following formulae:

Patented. Dec. 31 1907.

The reac-- The new product is soluble in concentrated sulfuric acid with a bluish-green color turning red on addition of water. It can be converted into a sulfonic acid dyeing unmordanted WOOl from an acid bath vio1etblue shades.

The 'sulfonic acid can be prepared as follows: One part of the before described condensation product is dissolved with 3 part of boric acid in 10 parts of fuming sulfuric acid containing 40% of sulfuric anhydrid. The solution is heated to 90 C. and fuming sulfuric acid containing of sulfuric anhydrid is gradually added until a test portion is completely soluble in dilute caustic soda. The sulfonic acid of the dyestufi is then precipitated by dilution of the melt with water and filtered off.

The process is carried out in a similar manner for the preparation of other of the above mentioned new compounds and for the production of the sulfonic acids therefrom.

In the following table the properties of s'zzasoo some of the materials used for the production of the new dyestuffs are given.

1 Solution in 1 Appearance. i i figg concentrated 1 y sulfuric acid.

1) l-acetylrnethylamino- Rusty red Orange. Slightly cole-aminoantln'aquinone. c 1' y s t a lored.

line powtier.

2) anthrapyridon ob- Green i sh- Orangc- Ye] l o w i sh tained from No. 1. (4- leaflets. red with with green amin o -1-anthrapyri a green- II n o r o s don). ish ,vel cence.

low fluorescence.

3) l-acetylmethyla mino- B r o w n i s l1 0 r a n g e- Almost col- 5-aminoanthraquinone. red crysred. orless.

t a l l i n e powder.

4) anth rapyridon oh- Brownerys- 0 ra n g e- Bro w n i :3 lltained from No. 3. (5- tals. yellow. yellow. a m in 0 -1-antb rapyridon).

In the following table the properties of some of the new dyestuffs are described:

NaOH) and heat the resulting mixture to 50 0. Enter 10 parts of cotton and dye in the Remove the goods, rinse vat for hour.

. Solution in Dyes unmorv Solution in The sullonic Condensation roduct from A earance. concentiated danted cotton v v P PP 1101: (11111101111. sulfuric {mi fromauvatj, aciddycseool.

l-aminoanthraquinone+4-b1'omo-1-anthrapyridon.... Dark brown Red ole dd h-W'W Violet.

prisms. let.

2-aminoanthraquinone+4-bromo-1-anthrapyridon.... Brown crys- Crimson red.. Violet Red Red.

tallmepowder.

5-amino-1-anthrapy1'idon+2-chloroanthraquinone.... Biorlvn crys- Orange Green Orange Orange.

2.G-diamino-anthraquinone+4-bromo-l-antlirapyri- Brown crys- Brownish-red. Violet-red.... Violet-red..... Violet.

on. talline powder.

1-oxy-4-aminoanthraquinone+4-bromo-1-anthrapy- Dark-blue Blue Greenish-blue. Violet Blue.

ridon. crystalline powder.

4-amino-1-anthrapyridon+4-bromo-1-antl1rapyridon.. Violetneedles. Violet BluiSh-green.. Violet-blue.

and soap hot. A very fast red shade is thus obtained. The process for dyeing is carried out in the same way on using others of the above mentioned dyestuffs. They produce the shades as described in the table. The dyestuffs in an analogous way are used for printing on cotton from a suitably thickened vat.

Having now described my invention and in what manner the same is to be performed, what I claim as new, and desire to secure by Letters Patent, is

1. The herein-described new anthracene derivatives which can be obtained from an.-

thrapyridons, which new derivatives are dark powders soluble in hot quinolin and in concentrated sulfuric acid, and which in the shape of their sulfonic acids dye wool from orange to red and blue shades, substantially as hereinbefore described.

2. The herein-described new anthracene. derivative which can be obtained by condensing 2 amino anthraquinone with 4- bromo 1 anthrapyridon, which new (1erivative is a brown powder soluble in hot quinolin with a crimson red color and in con centrated sulfuric acid With a Violet color,

PAUL THOMASCHEWSKI.

Witnesses:

OTTO KoNIG, WM. WASHINGTON BRUNswIoK. 

